Patent GB-358534-A (GB)
Title: Improvements in the manufacture and production of polymerisation products
IPC: C08F2/22
Filed: 1930-05-06
Abstract: The polymerization of water-insoluble saponifiable derivatives of acrylic and a -methyl acrylic acid such as esters, nitrite amide or amilide of acrylic acid or esters or amide of -methyl acrylic acid is effected by emulsifying these substances as such or in admixture with one another or with other substances which may be polymerizable, and then polymerizing by known processes, the products being in the form of latex which when coagulated resemble rubber.  The emulsions may be prepared with emulsifying or wetting agents such as Marseilles soap, ammonium oleate or Turkey red oil, alkylated naphthalene sulphonic acid salts, or palmitic sulphonic acid salts.  The polymerization may be effected at raised temperature and pressure in closed vessels and may be facilitated by irradia-tion, by polymerizing agents such as hydrogen peroxide, ozone, benzoyl peroxide or sodium p-toluene sulphonic chloramide.  Other organic substances capable of forming films or polymerizing to form film-forming products, may be added to the emulsions, such as vinyl acetate or chloride, styrene, cellulose derivatives, rubber, synthetic resins such as p-toluene sulphonamide-formaldehyde resins or polymers of styrene or vinyl acetate, or softening agents such as camphor, phenols, phthalic esters, phosphoric esters, urea derivatives, or like known plasticizers, the cellulose derivatives &c. being preferably dissolved in the acrylic acid derivatives before emulsification. The acrylic acid derivatives may be slowly introduced by spraying or dropping into water or aqueous solutions of emulsifying agents while stirring or whirling and heating and/or irradiating.  The polymerized products may be used alone as adhesives for safety glass or as coatings on leather or fabrics; or may be used in admixture with cellulose nitrate, carboxylates, or ethers for the production of flexible films; and when they contain vinyl chloride or styrene may be used for film, threads or coatings, and with a proportion of 80 per cent or more of vinyl chloride or styrene artificial masses of high electrical insulating power may be made by pressing.  In the examples (1) acrylic methyl ester is emulsified with aqueous Marseilles soap sodium propyl naphthalene sulphonate and hydrogen peroxide at 80-90 per cent, unpolymerized ester being removed by steam; the emulsion is coagulated by hydrochloric acid; (2) acrylic ethyl ester is emulsified with the mono-oleic ester of triethanolariol and polymerized; (4) styrene and acrylic ethyl ester are emulsified with Turkey red oil and sodium isobutyl naphthalene sulphonate and polymerized; (6) cellulose nitrate is dissolved in acrylic ethyl ester and emulsified with Marseilles soap and sodium isobutyl naphthalene sulphonate at pH=6,2, hydrogen peroxide being then added and the mixture polymerized; a -methyl acrylic butyl ester containing benzoyl peroxide is emulsified with Turkey red oil and sodium isobutyl naphthalene sulphonate and polymerized; (8) acrylic nitrile is emulsified with the sodium salt of palmitic sulphonic acid and Marseilles soap and hydrogen peroxide; the product precipitates as a powder and can be moulded by pressure yielding strong insulating masses; an emulsion of acrylic nitrile and acrylic ethyl ester is polymerized; an emulsion of acrylic nitrile and acrylic methyl ester with benzoyl peroxide, Turkey red oil and sodium di-isobutyl naphthalene sulphonate is polymerized, and coagulated by hydrochloric acid; the product dissolves in concentrated acids such as phosphoric acid with saponification, for example as in Specification 351,508, and is suitable for moulding by pressing; (11) an emulsion of acrylic nitrile and vinyl acetate is polymerized and treated with steam for example as in Specification 351,508; (12) an emulsion of acrylic nitrile and styrene is polymerized; (13) an emulsion of acrylic nitrile acrylic methyl ester, and styrene is polymerized at 100-100 DEG  C. in a stirring autoclave, a rubber-like product being obtained which is hardened by hydrochloric acid; a solution in acetone may be converted into artificial silk by dry spinning; (14) an emulsion of acrylic ethyl ester and acrylic acid is polymerized and treated with steam to yield a hard mass; (15) the polymer obtained in Example 3 or 5 with an equal quantity of cellulose nitrate is dissolved in a mixture of ethyl and methyl acetates and methanol and used for the production of films; (16) equal parts of the product of Example 3 or 5 and of cellulose nitrate are dissolved in acetone and spun through a tower 1,2 metres high at 85 DEG  C. through spinning nozzles at a pressure of 8 atmospheres and a drawing-off velocity of 137 metres per minute, the finished threads being denitrated in the usual manner; (17) an emulsion of acrylic nitrile, acrylic methyl ester and camphor is polymerized, and coagulated with hydrochloric acid; the product is hard but thermoplastic and can be moulded or blown like celluloid; instead of camphor there may be used tricresyl phosphate, phenol, dibutyl phthalate or diphenyl- or dimethyl-urea; (18) acrylic nitrile is dropped slowly into an aqueous solution of sodium isobutyl naphthalene sulphonate, Turkey red oil and hydrogen peroxide at 90-95 DEG  C. under reflux, while stirring, the product precipitating as a powder; (19) acrylic nitrile containing benzoyl peroxide is sprayed into an aqueous solution of sodium isobutyl naphthalene sulphonate and Turkey red oil at 90 DEG  C.; (2) acrylic ethyl ester is dropped slowly into an aqueous solution of sodium oleate, the monooleic ester of triethanolamine and hydrogen peroxide, the latex-like product being precipitated by steam; (22) acrylic methyl and ethyl esters and acetic anhydride are sprayed into aqueous Marseilles soap, Turkey red oil and hydrogen peroxide, the product being coagulated by steam or sulphuric acid; (23) acrylic nitrile, acrylic ethyl ester and vinyl acetate are slowly introduced into aqueous Turkey red oil, sodium isopropyl naphthalene sulphonate and hydrogen peroxide; (24) acrylic nitrile containing tri-(chlorethyl) phosphoric ester and benzoyl peroxide is gradually introduced into aqueous sodium isobutyl naphthalene sulphonate and Turkey red oil, the product being treated with steam, for instance as in Specification 351,508, yielding a powder; (25) a mixture of acrylic nitrile, acrylic acid, and acetic anhydride is introduced into aqueous octodecyl alcohol sulphuric ester, Turkey red oil and hydrogen peroxide; (26) acrylic ethyl ester containing acetic anhydride and benzoyl peroxide is introduced into aqueous Marseilles soap and Turkey red oil in bright sunlight, the product being insoluble in organic solvents.ALSO:The polymerization of water-insoluble saponifiable derivatives of acrylic and a -methyl acrylic acid such as esters, nitrile amide or anilide of acrylic acid or esters or amide of a -methyl acrylic acid is effected by emulsifying these substances as such or in admixture with one another or with other substances, which may be polymerizable, and then polymerizing by known processes, the products being in the form of latex which when coagulated resemble rubber.  The emulsions may be prepared with emulsifying or wetting agents such as Marseilles soap, ammonium oleate or Turkey red oil, alkylated naphthalene sulphonic acid salts, or palmitic sulphonic acid salts.  The polymerization may be effected at raised temperature and pressure in closed vessels and may be facilitated by irradiation, by polymerizing agents such as hydrogen peroxide, ozone, benzoyl peroxide, or sodium p-toluene sulphonic chloramide.  Other organic substances capable of forming films or polymerizing to form film-forming products, may be added to the emulsions, such as vinyl acetate, or chloride, styrene, cellulose derivatives, rubber, synthetic resins such as p-toluene sulphonamide-formaldehyde resins or polymers of styrene or vinyl acetate, or softening agents such as camphor, phenols, phthalic esters, phosphoric esters, urea derivatives, or like known plasticizers, the cellulose derivatives &c. being preferably dissolved in the acrylic acid derivatives before emulsification. The acrylic acid derivatives may be slowly introduced by spraying or dropping into water or aqueous solutions of emulsifying agents while stirring or whirling and heating and/or irradiating.  The polymerized products may be used alone as adhesives for safety glass or as coatings on leather or fabrics; or may be used in admixture with cellulose nitrate carboxylates or ethers for the production of flexible films; and when they contain vinyl chloride or styrene may be used for films, threads, or coatings, and with a proportion of 80 per cent or more of vinyl chloride or styrene artificial masses of high electrical insulating power may be made by pressing.  In the examples (1) acrylic methyl ester is emulsified with aqueous Marseilles soap, sodium propyl naphthalene sulphonate, and hydrogen peroxide at 80-90 DEG  C., unpolymerized ester being removed by steam; the emulsion is coagulated by hydrochloric acid; (2) acrylic ethyl ester is emulsified with the monooleic ester of triethanolamine and polymerized; (4) styrene and acrylic ethyl ester are emulsified with Turkey red oil and sodium isobutyl naphthalene sulphonate and polymerized; (6) cellulose nitrate is dissolved in acrylic ethyl ester and emulsified with Marseilles soap and sodium isobutyl naphthalene sulphonate at pH = 6,2, hydrogen peroxide being then added and the mixture polymerized; a -methyl acrylic butyl ester containing benzoyl peroxide is emulsified with Turkey red oil and sodium isobutyl naphthalene sulphonate and polymerized; (8) acrylic nitrile is emulsified with the sodium salt of palmitic sulphonic acid and Marseilles soap and hydrogen peroxide; the product precipitates as a powder and can be moulded by pressure yielding strong insulating masses; an emulsion of acrylic nitrile and acr